Anticorrosion composition



y 1946- J. J. MISKEL 2,403,293

ANTICORROSION COMPOSITION Filed June 5, 1943 5 LEGEND E|- COMPQ'A'ZWETSTEEL COMPQ'A," DRY STEEL COMPO5"B& "A", WET 5TEEL O COMPO'C", WET STEEL03 DD: /x O G I A QK/O/ o if 48 72 96 320 TIME, HOURS INVENTOR BY WfiMATTORNEY Patented July 2, 1946 ANTICORDOSION COMPOSITION John JosephMiikel, Brooklyn, N. Y., alsignor to National Oil Products Company,Harriso a corporation of New Jersey Application June 5, 1943, Serial No.489,784

Claims. 1

This invention relates to temporary oily and greasy coatings forapplication to metallic obiects to prevent the corrosion thereof, andmore particularly to such compositions containing surface-active fattyamino compounds.

It is the practice in the metal-working industry to coat finished orsemi-finished metallic components with oily or greasy composition topreserve them from corrosion during subsequent working, storage orshipment. This practice is highly necessary, but entails a considerableinconvenience. For instance. when using oily compositions for thispurpose. it is necessary to thoroughly dry the metallic obiects to betreated before applying the corrosion-proofing coating thereto, sinceotherwise any water on the surface of the objects will be entrapped andwill cause local corrosion. Since metallic obiects are almost alwayspickled, phosphated. plated, blacked, anodined, etc., as a final step inthe manufacture thereof, this necessity for careful drying occurs veryfrequently, and consumes a vast amount of time, equipment, space andlabor in the metal working industries. Further, even though a metallicsurface may be macroscopically dry, it frequently carries an absorbedsurface film of moisture, which materially reduces the eflectiveness ofthe various rust proofing compounds hitherto employed.

Accordingly, it is an obiect of this invention to provide oilycorrosion-proofing compositions which may be applied to wet metallicobjects, and which will displace the water on the surface thereof toprovide a corrosion-proofing film directly in contact with the metal.

Another object is to provide corrosion-proofing compositions which willpenetrate and displace the microscopic film of adsorbed moisture almostuniversally occurring on the surfaces of metallic objects so as toprovide a more effective anticorrosion film.

Another obiect is to provide rust proofing compositions of the typesoutlined above which will be cheaply and readily made from cheaply andreadily procurable raw materials.

The foregoing and other objects are achieved in accordance with thisinvention by the incorporation into an oily composition designed forapplication to metallic surfaces for corrosionfatty amine compound. Suchan amino compound will impart to the composition the property ofdisplacing any moisture whether in the form of macroscopic water dropsor in the form of an adsorbed vapor film on any metallic surface so asto form an oily coating in immediate molecular contact with the metallicsurface and to prevent the corrosion thereof.

The oily or greasy bodies to which fatty amino compounds are addedaccording to this invention may be substantially the same as thosehitherto employed for corrosion proofing coatings, which usually consistof petroleum or fatty oils or mixtures of petroleum or fatty oils,usually with the petroleum oil, which is cheaper, in predominantproportion. Suitable petroleum oil are any naphthenic or paraflinicpetroleum oils of sufficiently low volatility, noncorrosiveness andviscosity to be suitable metal-coating agents. Suitable fatty olls arethe animal. marine and vegetable oils, and preferably the fatty acidsderived therefrom. Examples of suitable fatty oil materials are spermoil, cod oil, train oil, pilchard oil. lard oil, ncats-foct oil, oliveoil. cottonseed oil. and the like; and fatty acid oils such a red oil,stearic acid, coconut fatty acids. fish oil fatty acid and the like.Likewise tall oil and naphthenic acids may be employed, since theypossess properties generally similar to those of the fatty acids.

As fatty amino compounds to be incorporated into oily and greasycorrosion-proofing compositions according to this invention there may beemployed any substances containing fatty chains of "surface active"length, i. e., having from about 10 to about 22 carbon atoms permolecule. and also containing one or more primary or secondary aminogroups. such as the higher fatty amines and amido-amines. Examples ofsuitable fatty amines include dodecyi amine, lauryl amine, palmityiamine, stearyl amine, oleyl amine and the like. Instead of compoundscontaining amino groups directly attached to the fatty carbon chain,there may be employed compounds in which the amino groups are on organicgroups attached by ether, ester or amide linkages to the fatty carbonchain. such compounds being represented, for instance, in theamide-amines on the order oi oleyl monoamide of diethylene trlamine, thestearyl proofing M0 of a small quantity of a higher monoamide ofdiethylene triamine, the oleyl monoamide of ethylene diamine, dodecylmonoamide of diethylene triamine, etc. Particularly favorable resultshave been secured by the use of of the oleyl monoamide of diethylenetriamine. Instead of the pure compounds there may. of course, beemployed mixtures containing one or more compounds coming within thequalifications above set forth, for instance, the fatty amines and fattyamide-amines derived from the natural oils, fats and waxes. Moreover.since the naphthenic acids and tall oil possess properties generall inline with those of the animal and vegetable fats and oils. the aminesand amide-amines containing the high molecular radlcles of thesematerials may likewise be employed. The amount of the fatty aminecompound incorporated into the only compositions of this invention maybe very small. mounts on the order of V4% to 1%, based on the total oilycomposition, being suflicient to secure results in accordance with thisinvention. Greater quantities may be added. as dictated by particularrequirements and economicconsiderations.

The corrosion-preventive oily and greasy compositions of this inventionmay be applied to metal components and other objects in the same manneras has been the practice with similar compositions in the past, 1. e. bydipping, spraying, mop ing. brushing, etc. However, in contrast to thepractice heretofore, it is unnecessary to insure absolute dryness of thesurfaces to be treated; in fact the compositions of this invention willactually displace macroscopic accumulations of water occurring on metalsurfaces and will effectively form a corrosion proofing film over themetal despite the former presence of the water. This property will beseen to result in a great saving of time and labor in the corrosionproofing of metallic objects. since it will be unnecessary to dry suchobjects after phosphating, pickling, blacking, anodizing, etc.,treatments; the object to be treated may simply be rinsed in water,drained free of the rinsed water insofar as this will spontaneously run011 and then, without further draining or inspection, immersed in theanticorrosion compositions of this invention. Somewhat lessspectacularly, the compositions of his invention have been found to formcorrosion preventing iilms upon metallic surfaces which are dry tovisual inspection, which films are of superior effectiveness as comparedto similar compositions heretofore prepared. This is no doubt due to thefact that metallic objects generally contain an adsorbed film ofmoisture which the compositions of the present invention are capable ofdisplacing but which the compositions of the prior practice simplyentrap.

Following are examples of compositions according to this invention, andof the use thereof, all parts given being by weight.

Example I In this and in succeeding examples, accelerated corrosiontests were conducted upon steel panels treated with compositionaccording to this invention and also, for purposes of comparison, uponsteel panels treated by other methods. The tests were conducted upontreated 4" x 6" panels of 18 gage SAE-1015CF steel. The panels weremounted upon a turntable which carried them alternately into a chambermaintained at 70 F. and 25% humidity and into a. chamber maintained at160-170 F. and 100% humidity,

this cycle being completed every 3 minutes. Condensation on the panelsoccurred in the moist chamber, and reevaporation in the dry chamber, ateach cycle, thus providing unusually severe corrosive conditions. Thesurface of each panel was examined periodically and the rust spots onthe entire surface of both faces of that panel were counted and taken asa measure of the corrosion of that panel, Obviously the less the numberof rust spots found at any given time upon a given test panel, the moreeifective the protection of that panel must have been. The corrosiveconditions encountered in this test may be taken to represent exposureto normal conditions of transportation and storage of 10 to 100 timesthe actual time of exposure in the apparatus.

The following rust-proofing coatings were prepared.

Composition A.-Not in accordance with this invention, merely forpurposes of comparison.

Parts Chromium soap of wool grease 20 V. M. & P. naphtha CompositionB.-In accordance with this invention.

Parts Tall 01] 8V2 Oleic monoamide oi ethylene diamine 1 Mineral oilComposition C.In accordance with this inl. A set of cleaned steel panelswere wet with water and then directly immersed while still wet inComposition A above. The panels were left in the composition for 10minutes and then withdrawn and allowed to drain for 60 hours. They werethen subjected to the accelerated corrosion test set forth above. Theaverage results of this corrosion test are recorded graphically in curve1 of the drawing and also in the table at the end of Example IVhereinbelow (item under Example I, paragraph 1"). It will be noted thatthe protection aflorded was only partial, since a considerable number ofrust spots developed almost immediately.

A set of cleaned steel panels were carefully dried and immersed inComposition A for 10 minutes. The panels were removed, allowed to drainfor 60 hours and then subjected to the accelerated corrosion test. Theaverage results are recorded graphically in curve 2 of the drawing andin the table hereinbelow (Example I, paragraph 2). It will be noted thatfair resistance to corrosion was provided by this treatment.

3. A set of cleaned steel panels were wet with water and dipped inComposition B, Thereafter they were removed from the composition B andimmersed tor minutes in Composition A. Therearter the panels wereremoved from Cornposition A, allowed to drain for 60 hours and thensubjected to the accelerated corrosion test,

hereinbelow ("Example I, paragraph 3") will be noted that the use ofComposition B, which contains iatty amide-amine (oleic monoamide ofethylene diamine) in this invention, resulted in superior performanceover the panels treated as described in the immediate preceding pragraph 2 although the panels or paragraphil were absolutely dry as faras could be determined by visual inspection whereas the panels treatedin accordance with this paragraph were initially wet with water.

4. A set of cleaned steel panels were preliminarily wet with water andwere immersed while still wet in Composition C for 10 minutes.Thereafter the panels were removed, drained for 60 hours and subjectedto the accelerated corrosion test, the average results oi which arerecorded graphically in curve 4 of the drawing and also in the tablehereinbelow (Example I, paragraph 4) (The long and elaborate soaking anddraining were merely for the purpose of insuring uniform testconditions, and are not necessary in the usual practice of thisinvention.) It will be seen that this composition gave outstandingperiormance, with only very gradual onset of any corrosion whatsoeverand very slight final corrosion, notwithstanding the loot that thepanels upon which this treatment was carried out were initially wet withwater.

EXAMPLE II Tsua'rm'rs COIIBIHID wr'ra Csus'rrc BLACKEIHNG Composition DParts Coumarone-indene resin 11.8 Lead soap 01' wool grease 3.2 Vistacpolyisobutylenes 1.0 Tall oil 3.4 Oleyl monoamide or diethylenetriamine- .6 V. M. 8: P. naphtha 80.0 100.0

"Vistas" is a trade name belonging to Advance Solvents and Chemical Coration designating mixed utylene having a molecular pol era of butyleneand loco) we ght between 1100 and 240 This example was carried out uponsteel panels which had been preliminarily cleaned and treated with acaustic blackening agent in order to show the cumulative effect ofcompositions according to this invention upon such blackened panels.which possess a certain amount of corrosion resistance aside from anyoil treatment. A number oi. steel panels were given a caustic blackingtreatment in a commercial solution (Ebonol manufactured by the EnthoneCompany, New Haven, Connecticut). This treatment was carried out byimmersing the panels for 40 minutes in the boiling "Ebonol" solution,the boiling point of which was maintained at 290 F. by periodicadditions oi water. The panels were then rinsed 3 times in cold water.

1. A set of panels treated with Ebonoi" as just described wereimmediately subjected to the accelerated corrosion test without furthertreat- 6 ment. As will be seen from the table hereinbelow ("Example II,paragraph 1), the panels were completely rusted at the end 0! the test.

2. A set oi panels treated with Ebonol as above set forth were dried insawdust and then immersed in Composition C of Example I for 10 minutes,drained for 24 hours and thereafter sub- Jected to the acceleratedcorrosion test. As will be seen from the table hereinafter (Example II,paragraph 2") only a slight amount of corrosion occurred within 500hours, at the end oi which time the test was discontinued.

3. A set of panels still wet irom the dual rinsing of the "Ebonoltreatment were directly immersed in Composition C for 10 minutes,removed, drained for 24 hours and subjected to the accelerated corrosiontest. Only slight corrosion resulted over the 500-hour period in whichthe test was conducted, see the table "mmple 11, paragraph 3."

4. A set of panels which had been subjected to the "Ebono treatment weredried in sawdust and immersed in Composition D for 10 minutes, removed,drained for 24 hours and thereafter suhiected to the acceleratedcorrosion test. Only slight corrosion resulted (table, "Example II,paragraph 4").

5. A set of panels still wet from the final rinse in" the Ebonoltreatment were immersed in Composition D for 10 minutes, removed,drained {or 24 hours and subjected to the accelerated corrosion test.Only minor corrosion resulted (table, Example II, paragraph 3") EXAMPLEIII TszA-rm'rs Comm wr'rn Prrosrns'rnw The procedure of Example 11 wasprecisely repeated. with the exception that the steel plates, instead ofbeing treated with Ebonol, were phosphated at 203 F. for 60 minutes in a"Parkerizing solution, which is a commercial phosphating compositionmanufactured by The Parker Rust-Proof Company. The results of thesetests are included in the table following Example IV, the items "ExampleIII, paragraph 1" to Example III, paragraph 5. It will be seen that ineach case the treatments of this invention greatly enhanced therecognized rust-proofing qualities of the Parkerizing treatment.

EXAMPLE IV Tmrmrs Counnmn wrrn Pnosrnsrmo The procedure of Examples IIand III was precisely repeated, with the exception that the steelpanels, instead of being treated with "Ebonol" or Parkerizing solution,"were phosphated at 200 F. for five minutes in a "Bonderizing solution,which is a commercial composition manufactured by the Parker Rust-ProofCompany. The results of these tests are included in the table iOlloWingthis example, the items Example IV, paragraph 1" to Example IV,paragraph 5. It will be seen that in each case the treatments of thisinvention greatly enhanced the recognized rust-proofing qualities of theBonderizing treatment. It will be appreciated, in connection with thisand the preceding two examples, that the ability to oil metal objectswhile still wet from rinsing after the Ebonol," Parkerizlng andBonderizlng treatments makes possible a great saving in time and labor.

Ann number of run spots on pouch ntreatmn: of 0m 0!! mm m m can an.ltilr. solar. our. man mar. W ill 8! Busted ms 14 as u I: 3 i i l i i 410 u 78 M o 0 o o 0 l o n o o 0 1 o 0 o o o 2 o 0 o o o a Busted o 0 o oo 2 o o 0 0 0 a o o o 0 o Ill-ted o o n 0 20 Rusted o o o 0 u 0 0 0 o o0 0 n o o l 2 is o o o 1 i a Oleyl amide oi diethylene triamine 1.5 Fesolvent 20.0

The foregoing was a very satisfactory slushing compound base which wascapable of further dilutlon with solvents for final application tovarious metallic surfaces such as steel, brass. copper, aluminum etc.When so applied. rust and/or corrosion was substantially completelyprevented on the treated surfaces.

' Trade name of Advance Solvents i. Chemical Co.

The above composition meets the Army and Navy Air Craft SpecificationARC-52 type 2, grade A, adapted for application to external surfaces inSavanna; Comm Parts Heavy mineral oil 71.0 Low melting point petrolatum25.0; Tali oil 3.4 Oleyl amide of diethylene triamine .6

The foregoing composition was a very satisfactory sloshing compound andwas found capable pounds are themselves cheaply and readily procurable.

I therefore claim:

1. An anticorrosion coating composition for metals comprising an oilymaterial containing a minor proportion, in an amount to function as ananticorrosive agent, of a fatty amido-amine containing fatty chains offrom 10-22 carbon atoms.

corrosive agent, of a fatty amide-amine containing fatty chains of from10-12 carbon atoms.

10-22 carbon atoms.

4. An anticorrosion coating composition for metals comprising chieflymineral oil and tail oil with a minor proportion, in an amount tofunction as an anticorrosive agent, of a fatty amide-amine containingfatty chains of from 10-22 carbon atoms.

5. An anticorrosion coating composition for metals comprising chieflymineral oil and a fatty oil with a minor proportion, in an amount tofunction as an anticorrosive agent, of the oleic acid monoamide ofdiethylene triamine.

8. An anticorrosion coating composition for metals comprising chieflymineral oil and tall oil and a minor proportion, in an amount tofunction as an anticorrosive agent, of the oleic acid monoamide ofdiethylene triamine.

7. A method of preserving wet metallic surfaces from corrosion whichcomprises coating said access:

10 maceswhiiestiilwctwithacompositioncomprising chiefly mineral oil andtall oil together with a minor proportion, in an amount to tunetion asan anticorrosive agent, of a fatty amideamine containing fatty chains offrom 10-22 carhon atoms.

10. A method of preserving wet metallic surfaces from corrosion whichcomprises coating said surfaces while still wet with a compositioncomprising chiefly mineral oil and tall oil together with a minorproportion, in an amount to function as an antlcorrosive agent, of theoleic acid monoamide oi diethyleno triamine.

Joan J.

Certificate of Correction Patent No. 2,403,293.

July 2, 1946.

JOHN JOSEPH MISKEL It is hereby certified that errors appear in theprinted specification of the above numbered patent requiring correctionas follows: Column 3, line 17, for only read 0113;; column 8, li.ne 50,claim 2, for "10-12 carbon atoms read 10-22 carbon atoms; and that thesaid Letters Patent should beread with these corrections therein thatthe same may conform to the record of the ease in the Patent Office.

Signed and sealed this 10th day of September, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

access:

10 surlaceswhiiestiilwetwithacompositioncomprising chiefly mineral oiland tall oil together with a minor proportion, in an amount to tunetionas an anticorrosive agent, of a fatty amideamine containing fatty chainsof from 10-22 carhon atoms.

10. A method of preserving wet metallic surfaces from corrosion whichcomprises coating said surfaces while still wet with a compositioncomprising chiefly mineral oil and tall oil together with a minorproportion, in an amount to function as an antlcorrosive agent, of theoleic acid monoamide oi diethylene triamine.

JOHN J. m.

Certificate of Correction Patent No. 2,403,293.

July 2, 1946.

JOHN JOSEPH MISKEL It is hereby certified that errors appear in theprinted specification of the above numbered patent requiring correctionas follows: Column 3, line 17, for only read 0113;; column 8, li.ne 50,claim 2, for "10-12 carbon atoms read 10-22 carbon atoms; and that thesaid Letters Patent should beread with these corrections therein thatthe same may conform to the record of the case in the Patent Office.

Signed and sealed this 10th day of September, A. D. 1946.

LESLIE FRAZER,

First Assistant Commissioner of Patents.

